Structure and properties of polypropylene crystallized from the glassy state

Glassy isotactic propylene (PP) films of thickness up to 0.3 mm were obtained by an ultraquenching technique. The structure and properties of the as-quenched and subsequently crystallized samples were characterized by various techniques. Electron microscopy indicates the glass has no structure larger than 25 Å. X-ray diffraction shows PP crystallizes from the glass into a smectic structure at ca. ?20°C and then transforms to monoclinic microcrystals at ca. 40°C; a nodular structure (80 to 100 Å in diameter) was observed on the surface. The transformation temperature increases with the film thickness. Annealing above the α-relaxation temperature results in an increase in the nodule size. A correspondence was found between the diameter of the nodules observed on the surface and long spacings obtained by small-angle X-ray scattering from the bulk. Dynamic mechanical spectra show the presence of two relaxation-like peaks at ca. ?10°C and 10°C for the as-ultraquenched samples. X-ray scattering, differential scanning calorimetry (DSC), and torsion pendulum measurements show PP crystallizes from the glass at a temperature, depending on the rate of heating, that corresponds to the lower relaxation peak temperature.     

Evaluation of polycarbonate substrate hologram recording medium regarding implication of birefringence and thermal expansion

In this paper, we evaluate photopolymer media using a polycarbonate (PC) substrate. In holographic data storage medium, substrates that sandwich the photopolymer material are needed to protect the photopolymer material against exogenous shock and open air. An optical glass such as BK-7 is normally used as a substrate, but a PC substrate has a cost advantage and is easy to fabricate compared with optical glass. For holographic recording and reading, however, the high birefringence and high thermal expansion of a PC substrate are significant problems. First, we analyze the degree of degradation of output power by the polarization change and estimate the threshold value of birefringence to record hologram normally. Next, we estimate the temperature tolerance of hologram readout with polycarbonate substrate hologram medium. These analyses results indicate the possible usage of the PC substrate as holographic recording media.     

Anisotropy of dielectric relaxation in crystal form II of poly(vinylidene fluoride)

The anisotropy of the crystalline relaxation (α relaxation) in oriented poly(vinylidene fluoride) in crystal form II has been studied. The dielectric increment Δε is analyzed on the basis of the two-site model. A linear relation between Δε/χξ and cos²θ is obtained, where χ is the degree of crystallinity, ξ is the ratio of the internal field to the applied field, and θ is the angle between the applied electric field and the molecular axis. The dipole moment changes direction only along the molecular axis in the relaxation in crystal form II; the molecular motion cannot be explained by chain rotation around the molecular axis. Possible models for the α relaxation are proposed: change in conformation with internal rotation can occur in the crystalline chains, and defects in the crystalline regions play an important role in the α relaxation.     

Coagulation of ferric oxide sol by organic solvents

Summary The coagulation of ferric oxide sol by several organic solvents, such as ethyl alcohol, has been studied. It has been observed that the coagulation takes place when the dielectric constant of medium is lowered to a certain critical value for coagulation by the addition of any organic solvent. The lowering of dielectric constant of medium is accompanied by the contraction of electrical double layer around sol particle, which leads to coagulation.

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Zusammenfassung Koagulation eines Ferrioxidsols durch verschiedene organische L?sungsmittel findet statt, wenn die Dielektrizit?tskonstante bis auf einen „kritischen” Wert durch Zufügung irgendeines organischen L?sungsmittels vermindert wird. Die Erniedrigung der DK des Mediums bedingt die Kontraktion der elektrischen Doppelschichten der Solpartikel, so da? Koagulation erfolgt.

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With 1 figure and I table     

Fluorescence probe for lysophospholipase C/NPP6 activity and a potent NPP6 inhibitor

Nucleotide pyrophosphatases/phosphodiesterases (NPPs) are ubiquitous membrane-associated or secreted ectoenzymes that have a role in regulating extracellular nucleotide and phospholipid metabolism. Among the members of the NPP family, NPP1 and -3 act on nucleotides such as ATP, while NPP2, -6, and -7 act on phospholipids such as lysophosphatidylcholine and sphingomyelin. NPP6, a recently characterized NPP family member, is a choline-specific glycerophosphodiester phosphodiesterase, but its functions remain to be analyzed, partly due to the lack of highly sensitive activity assay systems and practical inhibitors. Here we report synthesis of novel NPP6 fluorescence probes, TG-mPC and its analogues TG-mPC(3)C, TG-mPC(5)C, TG-mPENE, TG-mPEA, TG-mPhos, TG-mPA, TG-mPMe, and TG-mPPr. Among the seven NPPs, only NPP6 hydrolyzed TG-mPC, TG-mPC(3)C, and TG-mPENE. TG-mPC was hydrolyzed in the cell lysate from NPP6-transfected cells, but not control cells, showing that it is suitable for use in cell-based NPP6 assays. We also examined the usefulness of TG-mPC as a fluorescence imaging probe. We further applied TG-mPC to carry out high-throughput NPP6 inhibitor screening and found several NPP6-selective inhibitors in a library of about 80,000 compounds. Through structure-activity relationship (SAR) analysis, we identified a potent and selective NPP6 inhibitor with an IC(50) value of 0.21 μM. Our NPP6-selective fluorescence probe, TG-mPC, and the inhibitor are expected to be useful to elucidate the biological function of NPP6.     

Development of a highly selective fluorescence probe for hydrogen sulfide

Hydrogen sulfide (H(2)S) has recently been identified as a biological response modifier. Here, we report the design and synthesis of a novel fluorescence probe for H(2)S, HSip-1, utilizing azamacrocyclic copper(II) ion complex chemistry to control the fluorescence. HSip-1 showed high selectivity and high sensitivity for H(2)S, and its potential for biological applications was confirmed by employing it for fluorescence imaging of H(2)S in live cells.     

Selective Ablation of β‐Galactosidase‐Expressing Cells with a Rationally Designed Activatable Photosensitizer

We have developed an activatable photosensitizer capable of specifically inducing the death of β‐galactosidase‐expressing cells in response to photoirradiation. By using a selenium‐substituted rhodol scaffold bearing β‐galactoside as a targeting substituent, we designed and synthesized HMDESeR‐βGal, which has a non‐phototoxic spirocyclic structure owing to the presence of the galactoside moiety. However, β‐galactosidase efficiently converted HMDESeR‐βGal into phototoxic HMDESeR, which exists predominantly in the open xanthene form. This structural change resulted in drastic recovery of visible‐wavelength absorption and the ability to generate singlet oxygen (¹O₂). When HMDESeR‐βGal was applied to larval Drosophila melanogaster wing disks, which express β‐galactosidase only in the posterior region, photoirradiation induced cell death in the β‐galactosidase‐expressing region with high specificity.